CN109897181A - A kind of preparation method of high molecular weight MQ silicone resin - Google Patents
A kind of preparation method of high molecular weight MQ silicone resin Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of high molecular weight MQ silicone resin.Comprise the concrete steps that Q monomeric silicic acid ester and M monomer chlorosilane are pre-mixed, the flow velocity of control addition water and reaction temperature maintain 5-15 DEG C of low temperature in the first prepolymerization step, then through second step prepolymerization, obtain prepolymer, catalyst is added to be condensed, obtain weight average molecular weight > 20000, transparent rate is high, molecular weight dispersion is good, the MQ silicone resin of size tunable, the product has additive amount few in practical applications, stability is high, solution rate is fast, it is well dispersed, the advantages that film forming is strong, it can be applied to pressure sensitive adhesive, liquid silastic, electron pouring sealant, the fields such as personal nursing and cosmetic product.
Description
Technical field
The present invention relates to organic siliconresin synthesis technical fields, and in particular to a kind of preparation side of high molecular weight MQ silicone resin
Method and application thereof.
Background technique
MQ silicone resin is by simple function group (M group) chain link R3SiO1/2With four-functional group (Q group) chain link SiO4/2It carries out
The special polysiloxanes of structure made of hydrolytic condensation.It is generally believed that the close orbicule of MQ silicone resin bilayer three-dimensional structure, the centre of sphere
Part is with Si-O chain link, the higher caged SiO of density2；Spherical shell part is by the smaller R of density3SiO1/2Layer is surrounded.MQ silicone resin
Special construction so that it becomes ideal reinforced filling of polymer in composite material, current research is mainly used for organosilicon
In pressure sensitive adhesive and liquid silastic.Particularly, MQ silicone resin is usually used in makeup formula.In these formulations, MQ silicone resin mentions
High pigment or other active constituents that are formulated are to the compatibility of skin, to generate relatively more permanent and abrasion resisting product.But low phase
To the MQ silicone resin of molecular mass, volatile and low viscosity characteristic makes it be not easy to save in the formulation again, is easy to decompose, very
Extremely uncontrolled when in use skin may be flowed through, limit its application in cosmetic composition.If adding thickener,
The decline and greasy skin feel of stretchability energy can then be brought.
Patent document CN101323667A discloses a kind of preparation side of LED encapsulated strengthening methyl vinyl MQ silicon resin
Method.Particular by water glass solution is added into concentrated hydrochloric acid, phenyl alkoxysilane, vinylsiloxane base are added after reaction
The ethanol solution of silane and methyl alkoxy silane is extracted after cohydrolysis, is taken upper layer oil reservoir, is done after washing to neutrality
Dry removing low-boiling-point substance is to get colorless and transparent product MQ silicone resin.But MQ silicone resin molecular weight obtained by the patent is still very low, and GPC is surveyed
Number average molecular weight is 2800 to 4100.
Patent document CN102191055B discloses a kind of preparation method of MQ silicone resin, is the poly- silicon oxygen of hydrolysis-condensation
Alkane, alkoxy silane and its homopolymer wash product to neutrality with solution with low pole or nonpolar solvent extraction, using subtracting
Press distillation and concentration up to MQ silicone resin.It is up to 6200 that GPC, which measures MQ silicone resin molecular weight,.
Patent document CN103724626 A discloses a kind of preparation method of novel MQ silicone resin.The patent is using admittedly
Body sodium metasilicate is reacted with halosilanes, makees raw material preparation MQ silicone resin significantly with more the sodium silicate solid of sexual valence advantage than waterglass
Reduce production cost；Reaction process does not use acid catalyst, reduces raw material composition, eliminates the numerous of processing acidic catalyst
Trivial operation；By-product is NaCl solid, is measured less and easy to handle；Simple process is easy to operate；It can be used for producing a variety of MQ silicone resin.But
The molal weight of MQ silicone resin obtained by the patent has certain limitations applicable field in 2000~8000g/mol.
101899157 B of patent document CN discloses a kind of preparation method of MQ silicone resin.The patent is with ethyl orthosilicate
For raw material, solid strong acid is catalyst, obtains liquid or solid MQ silicone resin through hydrolytie polycondensation.It is to urge due to using solid strong acid
Agent can be directly filtered to remove after reaction, not need complicated last handling process, technical process is simpler, high production efficiency.But
Since strong solid acid catalyst is at high price, cause production cost higher, it is difficult to promote；And the patent be not directed to how
Control the partial size of MQ silicone resin.
Patent document CN104910382B discloses a kind of preparation method of MQ silicone resin, including is added in the reaction vessel
Deionized water, alcohol, esters of silicon acis and end-capping reagent stir to get emulsifying reaction system, and temperature is 20-55 DEG C, are passed through hydrogen chloride gas
Body 5-15min.After the reaction was completed, stratification takes lower layer's pre-polymerization resin layer, 120-150 DEG C is warming up to, 300-2000Pa's
Volatile component is removed under vacuum condition, obtains colorless and transparent MQ silicone resin.But the patent does not refer to the molecular weight of MQ silicone resin, and
And need to be passed through hydrogen chloride during the preparation process, there is corrosiveness to equipment, there is also certain security risks to operator.
European patent document EP1016685A2 discloses a kind of method for preparing super high molecular weight MQ silicone resin, specifically
Graft copolymerization is carried out with A, B macromolecule with special groups to obtain.Although obtaining MQ silicone resin weight average molecular weight can achieve
100,000 or more, but the macromolecule prepolymer component of obtained A and B in advance is needed, preparation process is complicated, with high costs.
Particularly, in MQ silicone resin as personal home care and cosmetic field, CN107468542A,
MQ silicone resin, but the MQ silicone resin of these patent disclosures have been used in CN108366924A, US6340466, WO97/17058
Molecular weight is not high, and film forming is bad, and is not disclosed to the data of its transparency.Patent CN1914251B is disclosed
A kind of MQ-T propyl siloxane resins, although gained resin molecular weight is high, preparation process is complicated, and has used dimethylbenzene
As solvent, for contacting the nursing materials such as skin and cosmetics receive limitation.
Therefore, dissolubility, dispersibility, the transparency are obtained using commercially available conventional raw material good, and the MQ silicone resin that molecular weight is high,
The technical issues of being this field urgent need to resolve.
Summary of the invention
To solve aforementioned technical problem, inventor is it has been unexpectedly found that using two sections of prepolymerizations, wherein first
Precondensation stage maintains prepolymerization reaction to carry out at low temperature, while controlling the addition speed of water, so that required water is 0.5 in reaction
It is at the uniform velocity added in~2h, subsequently into the second precondensation stage, wherein in the second precondensation stage, when increasing temperature the reaction was continued one section
Between, it can effectively improve the molecular weight of obtained MQ silicone resin, and gained MQ silicone resin molecular weight distribution is relatively narrow, transparency is good.
In addition, inventor has also been unexpectedly discovered that the high molecular weight MQ silicone resin being prepared using the present invention, selection screening is suitable
Spray dryer operating condition, size tunable, and the solid powdery high molecular weight MQ of favorable dispersibility has been prepared
Silicone resin.In practical applications, since the solid powdery MQ silicone resin molecular weight of the invention being prepared is high, molecular weight distribution
Relatively narrow, transparent good, favorable dispersibility, and size tunable, can be applied to pressure sensitive adhesive, liquid silastic, electron pouring sealant etc.
Field.Solid powdery MQ silicone resin especially of the present invention has additive amount few, and transparency is high, and stability is good, and solution rate is fast,
It is well dispersed, the advantages that film forming is strong, it is highly suitable for personal care product and cosmetics.
Above-mentioned purpose to realize the present invention, the invention is realized by the following technical scheme:
A kind of preparation method of MQ silicone resin, it is characterised in that: two sections of prepolymerizations are used, wherein in the first pre-polymerization rank
Section during the preparation process first premixes M monomer halosilanes and Q monomeric silicic acid ester, and prepolymerization reaction is maintained to carry out at low temperature,
It is added slowly with stirring water, subsequently into the second precondensation stage, wherein in the second precondensation stage, increases temperature to 60-90 DEG C,
Reaction time 2-4h.
Preferably, described method includes following steps:
(1) it pre-mix stage: maintains temperature at 5-15 DEG C, M monomer halosilanes and Q monomeric silicic acid ester is stirred colorless and transparent
System；
(2) first precondensation stages: maintaining the low temperature of pre-mix stage, be added slowly with stirring water, continues after adding anti-
Answer 0-30min；
(3) second precondensation stages: being added organic solvent, is warming up to 60~90 DEG C, 2~4h of reaction reacts, stratification；
(4) polymerization stage: catalyst is added in the pre-polymerization resin layer for taking lower layer to obtain after concentration, stirring heating is polymerize
Reaction, stratification remove lower layer's aqueous layer；
(5) post-processing stages: upper organic layer finally obtains high molecular weight MQ silicone resin by washing, filtering, concentration.
Preferably, the esters of silicon acis is selected from methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester and their oligomer
One of or a variety of mixing.
Preferably, halosilanes molecular formula is R1R3R4SiX, R1、R3And R4It is independently selected from alkyl, alkenyl, alkynyl and aryl, institute
Stating atomic number of alkyl carbon is 1-6, and alkenyl, alkynyl carbon atom number are 2-6, aryl carbon atoms 6-20；X is halogen atom.
It is further preferred that halosilanes R1R3R4In SiX, alkyl be selected from methyl, ethyl or propyl, alkenyl be selected from vinyl,
Acrylic or cyclobutenyl, alkynyl are selected from acetenyl, propinyl or butynyl, and aryl is selected from phenyl；X is selected from chlorine or bromine.
Still further preferably, halosilanes R1R3R4SiX is preferably trim,ethylchlorosilane, dimethyl ethyl chlorosilane, ethylene
Base dimethylchlorosilane, 3,5-dimethylphenyl chlorosilane, one of tri-phenyl chloride or a variety of mixtures.
Preferably, organic solvent be methanol, ethyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, toluene, dimethylbenzene, six
One of tetramethyldisiloxane or a variety of mixing.
Preferably, the concentration, which refers to, is concentrated into resin content 50-60wt% under heating condition.
Preferably, the water molar ratio in halosilanes, esters of silicon acis and step (2) be 1:2~6:0.5~3, preferably 1:2~
4:0.8~1.5.
Preferably, the water of the step (2) includes pure water, distilled water, deionized water or ultrapure water；Being slowly added to water is
Refer to that using feeder control water be at the uniform velocity to be added, speed control is added and is added in 0.5~2h, preferably 1~2h.
Preferably, catalyst is selected from the concentrated sulfuric acid, and trifluoromethanesulfonic acid, potassium hydroxide, zinc naphthenate, zinc Isoocatanoate works as catalysis
Agent is the concentrated sulfuric acid, and when trifluoromethanesulfonic acid, the dosage of catalyst is 0.1~0.5wt% of chlorosilane and esters of silicon acis summation；Work as catalysis
Agent is potassium hydroxide, zinc naphthenate, when zinc Isoocatanoate, catalyst amount be chlorosilane and esters of silicon acis summation 0.5~
1.0wt%.
The reaction temperature of the polymerization stage of the step (3) is 80-110 DEG C, reaction time 1-4h；The step (3) and
The concentration of step (4) refers at 110-150 DEG C, is concentrated into resin content 50-60wt%.
If desired, high molecular weight MQ silicone resin produced by the present invention can also be prepared as to the solid powder of size tunable
Shape product.Specific method is to be passed through spray dryer to be dried, the spray dryer band sub-cooled circulatory system, dry
Nitrogen is carrier gas, flow velocity 5-30L/min, preferably 10-20L/min, charging rate 0.5-10Kg/min, preferably 2-6Kg/
min.Obtaining solid powdery high molecular weight MQ silicone resin, median D50 is 5-15 μm, preferably 5-8 μm, Particle dispersity
PDI is 0.5-0.8.
It should be appreciated by those skilled in the art that MQ silicone resin of the present invention may include the R of limited quantity2SiO2/2
And RSiO3/2(respectively D chain link and T chain link).The limited quantity refers to can be containing no more than 10mol% in MQ silicone resin
D chain link and T chain link.
Compared to the prior art the present invention, has the advantage that 1, high molecular weight MQ silicone resin weight produced by the present invention is equal
Molecular weight is greater than 20000, applied to individual/household care products or the formula of cosmetics, has excellent spreading property, at
Film property is good, is not easily stripped and falls off, and has the good transparency, improves the using effect of nursing materials and cosmetics.2,
The present invention uses spraying method, directly obtains the solid product of required partial size, without doing further subsequent complexity to product
Processing step, by test, product particle is uniform, favorable dispersibility, and has accomplished solvent recovery simultaneously.3, the present invention uses
Raw material is commercial goods, and high molecular weight MQ silicone resin preparation method is simple, facilitates operation, cheap, has very strong city
Field promotional value.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, to better understand the invention.
The preparation of high molecular weight MQ silicone resin
Embodiment 1
(1) system temperature is maintained at 10 DEG C, 1.5mol trim,ethylchlorosilane and 3.5mol is being added just in the reaction vessel
Silester stirs to obtain colorless and transparent system；
(2) maintaining reaction temperature is at 10 DEG C, and in 1h, stirring is lower to be added 1.2mol deionization with feeder uniform speed slow
Water, the reaction was continued after adding 30min；
(3) 3mol ethyl alcohol is added, is warming up to 70 DEG C, reacts 3h, stratification；
(4) the pre-polymerization resin layer for taking lower layer to obtain is concentrated into resin content 60wt% at 120 DEG C, and 0.92g trifluoro is added
Methanesulfonic acid is warming up to 100 DEG C as catalyst, stirring, reacts 3h, and stratification removes lower layer's aqueous layer；
(5) upper organic layer is washed with deionized to neutrality, and filtering obtains colourless transparent liquid, is concentrated at 130 DEG C
Resin content is about 50wt%, obtains colourless transparent liquid shape product, as product MQ silicone resin.The items of gained MQ silicone resin
Performance parameter are as follows: it is about 10600 that GPC, which measures number-average molecular weight, and weight average molecular weight is about 23400, and dispersed PDI=2.21 is turbid
Spend 1.6NTU.
Embodiment 2
(1) temperature of system is maintained at 10 DEG C, in the reaction vessel be added 1.5mol dimethyl ethyl chlorosilane and
4.8mol ethyl orthosilicate stirs to obtain colorless and transparent system；
(2) maintaining reaction temperature is at 10 DEG C, and in 2h, stirring is lower to be added 1.8mol deionization with feeder uniform speed slow
Water, the reaction was continued after adding 10min；
(3) 4mol isopropanol is added, is warming up to 75 DEG C, reacts 4h, stratification；
(4) the pre-polymerization resin layer for taking lower layer to obtain is concentrated into resin content 60wt% at 120 DEG C, and 1.23g trifluoro is added
Methanesulfonic acid is warming up to 110 DEG C as catalyst, stirring, reacts 3h, and stratification removes lower layer's aqueous layer；
(5) upper organic layer is washed with deionized to neutrality, and filtering obtains colourless transparent liquid, dense under the conditions of 130 DEG C
Being reduced to resin content is about 55wt%, obtains colourless transparent liquid shape product, as product MQ silicone resin.Gained MQ silicone resin
Various performance parameters are as follows: it is about 11600 that GPC, which measures number-average molecular weight, and weight average molecular weight is about 24800, dispersed PDI=
2.14, turbidity 1.5NTU.
Embodiment 3
(1) temperature of system is maintained at 5 DEG C, in the reaction vessel be added 1.5mol 3,5-dimethylphenyl chlorosilane and
4.2mol methyl orthosilicate stirs to obtain colorless and transparent system；
(2) maintaining reaction temperature is at 5 DEG C, and in 1h, stirring is lower to be added 2.1mol deionized water with feeder uniform speed slow,
The reaction was continued after adding 20min；
(3) 3.7mol isobutanol is added, is warming up to 70 DEG C, reacts 4h, stratification；
(4) the pre-polymerization resin layer for taking lower layer to obtain is concentrated into resin content 55wt% at 120 DEG C, and 6.7g hydrogen-oxygen is added
Change potassium as catalyst, stirring is warming up to 100 DEG C, reacts 3h, and stratification removes lower layer's aqueous layer；
(5) upper organic layer is washed with deionized to neutrality, and filtering obtains colourless transparent liquid, dense under the conditions of 120 DEG C
Being reduced to resin content is about 55wt%, obtains colourless transparent liquid shape product, as product MQ silicone resin.Gained MQ silicone resin
Various performance parameters are as follows: it is about 9300 that GPC, which measures number-average molecular weight, and weight average molecular weight is about 21800, dispersed PDI=2.34,
Turbidity 1.5NTU.
Embodiment 4
(1) temperature of system is maintained at 15 DEG C, in the reaction vessel be added 1.6mol dimethyl ethyl chlorosilane and
4.3mol positive silicic acid propyl ester stirs to obtain colorless and transparent system；
(2) maintaining reaction temperature is at 15 DEG C, and in 2h, stirring is lower to be added 1.3mol deionization with feeder uniform speed slow
Water；
(3) 3mol ethyl alcohol is added, is warming up to 90 DEG C, reacts 3h, stratification；
(4) the pre-polymerization resin layer for taking lower layer to obtain is concentrated into resin content 57wt%, and 1.48g trifluoromethanesulfonic acid is added and makees
For catalyst, stirring is warming up to 100 DEG C, reacts 3h, and stratification removes lower layer's aqueous layer；
(5) upper organic layer is washed with deionized to neutrality, and filtering obtains colourless transparent liquid, dense under the conditions of 120 DEG C
Being reduced to resin content is about 60wt%, obtains colourless transparent liquid shape product, as product MQ silicone resin.Gained MQ silicone resin
Various performance parameters are as follows: it is about 9600 that GPC, which measures number-average molecular weight, and weight average molecular weight is about 22500, dispersed PDI=2.34,
Turbidity 1.6NTU.
Embodiment 5
(1) temperature of system is maintained at 10 DEG C, 1.6mol trim,ethylchlorosilane and 3.3mol is added in the reaction vessel
Ethyl orthosilicate stirs to obtain colorless and transparent system；
(2) maintaining reaction temperature is at 10 DEG C, and in 1h, stirring is lower to be added 1.9mol deionization with feeder uniform speed slow
Water, the reaction was continued after adding 30min；
(3) 3.2mol hexamethyldisiloxane is added, is warming up to 80 DEG C, reacts 3h, stratification；
(4) the pre-polymerization resin layer for taking lower layer to obtain is concentrated into resin content 55wt%, and 1.24g trifluoromethanesulfonic acid is added and makees
For catalyst, stirring is warming up to 100 DEG C, reacts 3h, and stratification removes lower layer's aqueous layer；
(5) upper organic layer is washed with deionized to neutrality, and filtering obtains colourless transparent liquid, dense under the conditions of 130 DEG C
Being reduced to resin content is about 56wt%, obtains colourless transparent liquid shape product, as product MQ silicone resin.Gained MQ silicone resin
Various performance parameters are as follows: it is about 11800 that GPC, which measures number-average molecular weight, and weight average molecular weight is about 26700, dispersed PDI=
2.26, turbidity 1.4NTU.
Embodiment 6
(1) temperature of system is maintained at 10 DEG C, 1.6mol trim,ethylchlorosilane and 3.3mol is added in the reaction vessel
Ethyl orthosilicate stirs to obtain colorless and transparent system；
(2) maintaining reaction temperature is at 10 DEG C, and in 1h, stirring is lower to be added 0.8mol deionization with feeder uniform speed slow
Water, the reaction was continued after adding 30min；
(3) 3mol isopropanol is added, is warming up to 80 DEG C, reacts 3h, stratification；
(4) the pre-polymerization resin layer for taking lower layer to obtain is concentrated into resin content 60%, and the conduct of 1.03g trifluoromethanesulfonic acid is added
Catalyst, stirring are warming up to 100 DEG C, react 3h, and stratification removes lower layer's aqueous layer；
(5) upper organic layer is washed with deionized to neutrality, and filtering obtains colourless transparent liquid, dense under the conditions of 130 DEG C
Being reduced to resin content is about 60wt%, obtains colourless transparent liquid shape product, as product MQ silicone resin.Gained MQ silicone resin
Various performance parameters are as follows: it is about 6500 that GPC, which measures number-average molecular weight, and weight average molecular weight is about 15200, dispersed PDI=2.34,
Turbidity 1.7NTU.
Embodiment 7
(1) temperature of system is maintained at 10 DEG C, in the reaction vessel be added 1.5mol 3,5-dimethylphenyl chlorosilane and
3.5mol ethyl orthosilicate stirs to obtain colorless and transparent system；
(2) maintaining reaction temperature is at 10 DEG C, and in 1.5h, stirring is lower to be added 3.0mol deionization with feeder uniform speed slow
Water, the reaction was continued after adding 30min；
(3) 3.5mol ethyl alcohol is added, is warming up to 90 DEG C, reacts 2h, stratification；
(4) the pre-polymerization resin layer for taking lower layer to obtain is concentrated into resin content 50wt%, and 1.21g trifluoromethanesulfonic acid is added and makees
For catalyst, stirring is warming up to 100 DEG C, reacts 3h, and stratification removes lower layer's aqueous layer；
(5) upper organic layer is washed with deionized to neutrality, and filtering obtains colourless transparent liquid, dense under the conditions of 130 DEG C
Being reduced to resin content is about 55wt%, obtains colourless transparent liquid shape product, as product MQ silicone resin.Gained MQ silicone resin
Various performance parameters are as follows: it is about 7200 that GPC, which measures number-average molecular weight, and weight average molecular weight is about 22600, dispersed PDI=3.14,
Turbidity 2.1NTU.
Comparative example 1
According to the same method of embodiment 1, the difference is that not controlled to the temperature of step (1) and step (2)
System.The various performance parameters of final gained MQ silicone resin are as follows: it is about 3600 that GPC, which measures number-average molecular weight, and weight average molecular weight is about
8700, dispersed PDI=2.42, turbidity 2.4NTU.
Comparative example 2
According to the same method of embodiment 1, the difference is that not in step (2) plus water speed control,
But it is directly mixed with raw material trim,ethylchlorosilane and ethyl orthosilicate.The various performance parameters of final gained MQ silicone resin
Are as follows: it is about 4300 that GPC, which measures number-average molecular weight, and weight average molecular weight is about 10600, dispersed PDI=2.46, turbidity 2.7NTU.
Embodiment 8The preparation of the high component MQ silicone resin of solid powdery
If desired, gained high molecular weight MQ silicone resin can also be passed through to the MQ silicon that size tunable is made in spray dryer
Resin.By taking 1 gained high molecular weight MQ silicone resin of embodiment as an example, the operating condition of spray dryer is that drying nitrogen is carrier gas,
Flow velocity 15L/min, the charging rate of spray dryer are 4Kg/min, the spray dryer band sub-cooled circulatory system.Final
To solid powdery high molecular weight MQ silicone resin, median (D50) is 5.3 μm, and Particle dispersity PDI is 0.62.It will be above-mentioned
The MQ silicone resin of embodiment 2-6 is prepared as solid powdery, each embodiment product cut size under the same conditions, with spray dryer
Controllably, and favorable dispersibility, the results are shown in Table 1:
Table 1
| Sample | Median D50 | Particle dispersity PDI |
| Embodiment 1 | 5.3μm | 0.62 |
| Embodiment 2 | 6.2μm | 0.63 |
| Embodiment 3 | 6.4μm | 0.65 |
| Embodiment 4 | 5.7μm | 0.62 |
| Embodiment 5 | 6.4μm | 0.57 |
| Embodiment 6 | 5.6μm | 0.76 |
| Embodiment 7 | 8.7μm | 0.94 |
Comparative example 1 and 2 gained MQ silicone resin of comparative example under the same conditions, the operation being spray-dried, but can not obtain
The solid powdery product controllable to uniform particle sizes.Reason may be because of comparative example 1 and the resulting MQ silicone resin of comparative example 2 point
Son amount is smaller, and the wider reason of molecular weight distribution.
Embodiment 9High molecular weight MQ silicone resin performance test
Further to verify the effect that gained high molecular weight MQ silicone resin is applied to personal nursing, cosmetic field, to it
Film forming etc. has carried out following tests, and sample is the solid powdery high molecular weight MQ silicate resinous product that embodiment 8 is prepared.
1. dissolubility is tested: 23 ± 2 DEG C of temperature, under humidity 40-80% environment, 5g powder MQ silicone resin is dissolved completely in
(size and uniformity of partial size are investigated, partial size is smaller, more uniform, dissolution the time required in five siloxanes ring body D5 of 20g decamethyl
Speed is faster), test result is shown in Table 2:
Table 2
| Sample | Dissolution time |
| Embodiment 1 | 7min |
| Embodiment 2 | 6min |
| Embodiment 3 | 7min |
| Embodiment 4 | 7min |
| Embodiment 5 | 5min |
| Embodiment 6 | 10min |
| Embodiment 7 | 12min |
| Comparative example 1 | 30min |
| Comparative example 2 | 40min |
2. toner compatibility test: 23 ± 2 DEG C of temperature, under humidity 40-80% environment, taking concentration is the resin-of 20wt%
D5 solution 35g is added H series-bright red toner of about 10 μm of 5g partial size of the good inhibition and generation of Germany, after stirring 5min, observes appearance
Uniformity, and the standard funnel test solution for being 0.5mm with aperture leaks down the time used completely to characterize mobility.Test result
It is as shown in table 3:
Table 3
3. film thickness is tested: by the above-mentioned resin solution 40g for being mixed with toner, being spread evenly across 30*50* with Bracewell coater
In the black leathers of 1mm (W*L*H), then being placed in 150 DEG C of baking ovens makes solvent volatilize completely, uses thickness measurement with laser after taking out cooling
Instrument tests film thickness.The testing experiment of feel test and grieshoch adhesiveness is carried out to obtained sample simultaneously, testing result is shown in as follows
Table 4:
Table 4
| Sample | Film thickness/μm | Feel | Dust |
| Embodiment 1 | 100 | It is smooth | Seldom |
| Embodiment 2 | 80 | It is smooth | Seldom |
| Embodiment 3 | 100 | It is smooth | Seldom |
| Embodiment 4 | 70 | It is smooth | Seldom |
| Embodiment 5 | 110 | It is smooth | Seldom |
| Embodiment 6 | 70 | It is more puckery | It is less |
| Embodiment 7 | 80 | It is more puckery | It is less |
| Comparative example 1 | 30 | It is coarse | It is more |
| Comparative example 2 | 40 | It is coarse | It is more |
As can be seen from the above data, for the MQ silicone resin obtained according to preparation method of the present invention due to molecular weight height, weight is equal
Molecular weight reaches 20000 or more, and molecular weight dispersion is good, and obtained grain is easy under the conditions of preferred spray dryer
Diameter is controllable, and the solid powder of good dispersion.To the obtained MQ silicone resin of the present invention have the effect of it is very excellent, in dissolubility
Extraordinary effect is obtained in test, toner compatibility test and film forming test.This is because what the present invention used
In preparation method, first choice premixes M monomer halosilanes and Q monomeric silicic acid ester, and maintains at low temperature, and water is added in control
Flow velocity carry out the reaction of prepolymer, and then avoid and increase suddenly in initial reaction stage reaction system viscosity, and then can prepare
Obtain high molecular weight MQ silicone resin.The MQ silicone resin that the present invention is prepared obtains partial size with can be convenient by boulton process
Controllable and favorable dispersibility solid powder product.Dissolubility is tested, in toner compatibility test and film forming test, this hair
The bright MQ silicone resin being prepared achieves good performance data, illustrates to be very suitable to individual/family care product, change
Adornment product.
The above specific embodiment only schematically illustrates the content of present invention, does not represent the limitation of the content of present invention.
It may occur to persons skilled in the art that be that specific structure can have other versions in the present invention.
Claims (10)
1. a kind of preparation method of high molecular weight MQ silicone resin, it is characterised in that the following steps are included: anti-using two sections of prepolymerizations
It answers, wherein during the preparation process, first premixing M monomer halosilanes and Q monomeric silicic acid ester in the first precondensation stage, remains pre-
Poly- reaction carries out at low temperature, is added slowly with stirring water, subsequently into the second precondensation stage, wherein in the second pre-polymerization rank
Section, increases temperature to 60-90 DEG C, reaction time 2-4h.
2. the preparation method of high molecular weight MQ silicone resin described in claim 1 comprising following steps:
(1) it pre-mix stage: maintains temperature at 5-15 DEG C, M monomer halosilanes and Q monomeric silicic acid ester is stirred into obtain colorless and transparent body
System；
(2) first precondensation stages: maintaining the low temperature of pre-mix stage, be added slowly with stirring water, the reaction was continued after adding 0-
30min；
(3) second precondensation stages: being added organic solvent, is warming up to 60~90 DEG C, 2~4h of reaction reacts, stratification；
(4) polymerization stage: catalyst is added in the pre-polymerization resin layer for taking lower layer to obtain after concentration, stirring heating polymerize anti-
It answers, stratification, removes lower layer's aqueous layer；
(5) post-processing stages: upper organic layer finally obtains high molecular weight MQ silicone resin by washing, filtering, concentration.
3. the preparation method of high molecular weight MQ silicone resin as described in claim 1, which is characterized in that halosilanes molecular formula is
R1R3R4SiX, R1、R3And R4It is independently selected from alkyl, alkenyl, alkynyl and aryl, the atomic number of alkyl carbon is 1-6, alkenyl, alkynyl
Carbon atom number is 2-6, aryl carbon atoms 6-20；X is halogen atom；The esters of silicon acis is selected from methyl orthosilicate, positive silicic acid
Ethyl ester, one of positive silicic acid propyl ester and their oligomer or a variety of mixing；
Preferably, halosilanes R1R3R4In X, alkyl is selected from methyl, ethyl or propyl, and alkenyl is selected from vinyl, acrylic or butylene
Base, alkynyl are selected from acetenyl, propinyl or butynyl, and aryl is selected from phenyl；X is selected from chlorine or bromine；Halosilanes R1R3R4X is preferably
Trim,ethylchlorosilane, dimethyl ethyl chlorosilane, vinyldimethylchlorosilane, 3,5-dimethylphenyl chlorosilane, triphenyl chlorine silicon
One of alkane or a variety of mixtures；The water includes pure water, distilled water, deionized water or ultrapure water.
4. the preparation method of high molecular weight MQ silicone resin as described in claim 1, it is characterised in that: halosilanes, esters of silicon acis and step
Suddenly water molar ratio is 1:2~6:0.5~3, preferably 1:2~4:0.8~1.5 in (2).
5. the preparation method of high molecular weight MQ silicone resin described in claim 1, it is characterised in that: step is slowly added to water in (2)
It is to use feeder to control water to be at the uniform velocity to be added, speed control is added and adds in 0.5~2h, preferably 1~2h.
6. the preparation method of high molecular weight MQ silicone resin according to claim 1, it is characterised in that: organic solvent be methanol,
Ethyl alcohol, isopropanol, one of n-butanol, isobutanol, the tert-butyl alcohol, benzene,toluene,xylene, hexamethyldisiloxane or a variety of
Mixing.The catalyst is selected from the concentrated sulfuric acid, trifluoromethanesulfonic acid, potassium hydroxide, zinc naphthenate, zinc Isoocatanoate；When catalyst is
The concentrated sulfuric acid, when trifluoromethanesulfonic acid, the dosage of catalyst is 0.1~0.5wt% of chlorosilane and esters of silicon acis summation；When catalyst is
Potassium hydroxide, zinc naphthenate, when zinc Isoocatanoate, catalyst amount is 0.5~1.0wt% of chlorosilane and esters of silicon acis summation.
7. the preparation method of high molecular weight MQ silicone resin according to claim 1, which is characterized in that the step (3) is gathered
The reaction temperature in conjunction stage is 80-110 DEG C, reaction time 1-4h；The concentration of the step (3) and step (4) refers in 110-
At 150 DEG C, it is concentrated into resin content 50-60wt%.
8. a kind of solid powdery high molecular weight MQ silicone resin is with the described in any item high molecular weight MQ of claim 1-7
Silicone resin is raw material, is passed through spray dryer and is dried, and obtains solid powdery high molecular weight MQ silicone resin, median
D50 is 5-15 μm, and preferably 5-8 μm, Particle dispersity PDI is 0.5-0.8.
9. solid powder high molecular weight MQ silicone resin according to any one of claims 8, which is characterized in that the operating condition of spray dryer
It is with the sub-cooled circulatory system, drying nitrogen is carrier gas, flow velocity 5-30L/min, preferably 10-20L/min, charging rate
For 0.5-10Kg/min, preferably 2-6Kg/min.
10. the purposes of solid powdery high molecular weight MQ silicone resin described in claim 8, which is characterized in that be used for individual/family
Care product or cosmetic product.
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Address after: 528441 No. 20, Jiexin Road, Shazi Industrial Park, Minmin Town, Zhongshan City, Guangdong Province Patentee after: Aiken silicone material (Zhongshan) Co.,Ltd. Address before: 528441 No. 20, Jiexin Road, Shazi Industrial Park, Minmin Town, Zhongshan City, Guangdong Province Patentee before: Zhongshan City Poly chemical materials Co.,Ltd. |